Paper treatment with apo and a polycarboxylic acid



Patented Jan. 9, 1968 United States Patent O "ce 3,362,850

1 to 10 carbon atoms, each of R and R is a hydrogen 3,362,850 atom or an alkyl group of from 1 to 10 carbon atoms and P PER T E MENT W T P N each of x and y is an integer of from to 10 such that PQLYCARBOXYLIC ACID th fi l l b l 'd r du t o t fro 32 to Duane L. Kenaga, Midland, Mich., assignor to The Dow 6 na po year Oxy 1c acl p o c C n ams m Chemiml Company Midland Mich a corporation of 5 120 carbon atoms per molecule. Repetition of the provi- Delaware ously-illustrated Diels-Alder reaction produces higher No Drawing Filed APL 17, 1964, sen 360,774 polycarboxylic acids. A preferred class of starting poly- 6 Clainm (CL 1 7 5 carboxylic acids may be obtained by the self-condensation of linoleic acid according to known methods (see US. 10 Patent 2,849,399 to Matuszak et al. and U.S. Patent ABSTRACT OF THE DISCLOSURE 3100784 Goebel) According to the process of the present invention, APO, Water repellent products are obtained by impregnating I a polycarboxylic acid of Formula I and a suitable anhythe P p with anhydrous Solutlons of y drous carrier are combined to prepare an impregnating P p oxide, known as and Certain p y composition. The untreated paper, cardboard or other y acids, as Catalysts, to g improved Strength, Wet paper product is then contacted with the impregnating burst, and wet tensile characteristics in the finished compgsjtion any onventional method uch as dipping Product. spraying or other known immersion processes. The impregnated material is then cured usually at a temperature This invention relates to a im roved thod f r o- Of 100 t0 190 C. for a time sufiicient t0 eifect substanducing paper products possessing good Wet strength and tially Complete Polymerization of the APO and p y water repellent properties, to compositions useful for this b0ltyhc acid p the Surface of the treated materialpurpose a d t d t f d h b M i Temperatures of from ambient room temperature (about larly, the present invention relates to the treatment of to y be used for Curing the impregnated paper and paper products with a mixture containing a non- P p ProduCtS- However, at room temperatures, the aromatic unsaturated polycarboxylic acid and tris (l-aziriing time required is usually from about one Week to dinyl)phosphjne oxide. days, and higher temperatures (120 to 190 C.) are pre- This(1-aziridinyl) h hine xide (APO) is l known ferred in order to shorten the curing times. The resulting as a textile treating agent which imparts flame resistance Product has excellent Water repenent Properties in addito textiles and has been suggested a a papgr treating 30 tion to gOOd wet strength characteristics. Neither agent as disclosed in US. Patents 2,891,877, 2,889,289, alone nor the polymerized fatty acids alene impart Water 2,859,134 and 3,034,919. In such known methods, howrepellent Properties to P p or P p Productsever, water repellency of the treated textiles is only ob- The treating compositions of the invention y tained by incorporating other known sizing reagents into taih P to 15 Percent y Weight of APO based p the h aqueous mixture containing O i d AP() total weight of the composition and the concentration of It has now been found that both increased wet strength the polyoafboXylie acid y be as high as 20 Percent y and Water repellency (sizing) is obtained when paper or based Upon the total of the composition. paper products are treated with mixtures of polyfunctional The Weight ratio of APO to polymerized fatty aeid y organic acids and APO in an anhydrous carrier medium vary from about 10010.1 to 0.1:100, respectively. Excelfollowed by curing the impregnated material at elevated 40 lent results are obtained When the Apoipolymefiled fatty temperatures, acid ratios are from about 20:1 to 1:10. At these ratios,

Th polycarboxylic id hi h are employed i h the total concentration of the combined APO-polycarprocess of the invention are polymers of unsaturated boXylie acid miXttlre y y from about to 10 P C C fatty acids and may be represented by the formula Cent y Vt/eight based p the total Weight of the treating K MI 5 composition.

The amount of the APO-polycarboxylic acid mixture wherein n is an integer of from about 2 to 6 (preferably which is deposited on the material to be treated may vary 2 to 4) and R is a hydrocarbon group of from 30 to 114 from .10 percent to 10 percent by weight based upon the carbon atoms which is derived from the corresponding dry product prior to treatment. The ratio of APOzpolyunsaturated monocarboxylic fatty acid starting material. carboxylic acid is essentially the same in the paper (or These polycarboxylic fatty acids are prepared accordother paper product) as it is in the treating solution being to the following reactions cause only relatively short contact times (up to /2 hour, (II) E H H H H H H000 R 1c'1'( 3R+Hooo R R f I H000-R C 1 n(HOOC\R1 o= --o=o-In) R--COOH H() (L ng-00011 e H R2 H wherein R is a non-aromatic hydrocarbon group of from depending on the size of the material) are used to impreg- 30 to 114 carbon atoms with a valence equal to the numnate the surfaces of the paper. The effects of preferential ber of carboxyl groups in the final compounds, R and R or selective absorption of the treating agents is therefore are each divalent alkylene or alkenylene groups of from minimized.

Any anhydrous solvent which does not react with the APO or the polycarboxylic acid may be used as a carrier in the process of the invention. Suitable solvents include conventional aliphatic hydrocarbon solvents such as hextween the sheet and the felt was used when the temperature during the cure cycle was recorded.

The handsheets were conditioned in a constant humidity room (relative humidity of 50 percent at 73 F.)

ane, heptane, etc., and aromatic hydrocarbon solvents 5 for 48 hours prior to testing. Wet and dry burst, wet and such as benzene, toluene and xylene. Halogenated soldry tensile and fold tests were run on specimens taken vents such as chlorobenzene, methyl chloroform, carbon from one 9 x 11 inch handsheet. Size tests were also run tetrachloride, chloroform, ethylene dichloride, ethylene (KBB size test). This test measures the time required dibromide and perchloroethylene, for example, may also to establish a flow of a given quantity of electrictty be employed. Other useful solvents include gasoline, kerom through a paper specimen placed between a lower zinc sene, dioxane, tetrahydrof-uran, dimethyl ether, anhydrous electrode and an upper, water soaked bronze electrode. methyl alcohol, acetone, methyl ethyl ketone, ethylben- Folding endurance is a measure of the strength of the zene and n-pentane. treated paper and is recorded as the total number of The use of water in the system is unsatisfactory befolds required to sever the paper at the crease when cause the APO-polycarboxylic acid mixture tends to po 15 a uniform folding rate (175 double folds per minute) lymerize before it can be deposited on the material to be is used. The test employed in the examples is known 35 treated. In addition, the polycarboxylic acids employed the Folding Endurance test and i ri d nare insoluble in water. The system of the invention can def TAPPI (T l A s ati n f r the Pulp and be used to treat any type of cellulose-based paper or Paper Industry) designation T423 m-SO. paper product (including paper board) and is not de- The burstlng strength of paper is defined as the hydropendent upon the type of pulp or process used to prepare static pressure (in pounds per square inch) required to the paper, rupture the material when pressure is applied at a con- The following examples are submitted for the purpose trolled increasing rate through a rubber diaphragm to a of illustration only and are not to be construed as limitcircular area of material 1.20 inches in diameter. The ing the cope of the invention in any way test is designated as TAPPI Standard T403 m-53. Both Wet and dry burst strength are measured by this method. Examples l-XXXIV The Wet burst strength is measured using a paper speci- Handsheets of unbleached Abitibi spruce kraft were men Whlch has been Soaked in dfliQnlZed Water for 24 di i ppp i h solutions containing hours at room temperature. Burst factors are calculated various ratios f U1l aziridinyl)phosphine Oxide and to correct for the basis Weight of each sheet to the standmixtures of polymerized fatty acids. The total amount 3rd TAPPI ream of f P Squaw of solids in the treating solution was maintained at 2 The P F are summanfid 111 m The P 3- percent by Weight based upon the Weight f the 1, carboxyhc acids used were mixtures of dimers and trimers lHrichloroethanQ h handsheets were immersgd in of lrnoleic acid. The compositton of each acid mixture 100 milliliters of the test solution for one minute. The used In tfil'ms of Percentage was as follows? sheets were then blotted and transferred to a chromeplated caul. After transfer, the impregnated sheet was Percent Percent Percent placed against a one-half inch felt pad and the total g 6 22 i assembly, felt-sheet-caul, was placed on the cold lower $4 platen of a press. The assembly, caul side up, was then 40 Acid com osmmr l raised against the hot upper platen for four minutes at A p Trace 75 25 a temperature of 190 C. with minimum pressure. The i 3% press was equipped with instruments for the control of temperature and cure times. A thermocouple placed be- Percent Composition of Example Treating Agents Wet Burst Dry Burst Wet Burst Number Acid Composition Size (Seconds) Factor (p.s.i.) Factor (p.s.i.) xmo lllS APO Poly Acid iControl) I (control) 100 O 8. 4 40. 5 83. 8 59. 7 II (control) 0 0 0.6 2. 1 67. 7 0. 0 I 95 5 8.0 41.4 75.3 51.1 85 15 144. 4 37. 7 s0. 7 55. 5 7o 30 15s. 1 3s. 9 75. 4 57. 4 55 135. s as. 8 s3. 7 57. 3 40 143. 4 2s. 5 77. s 42. 2 25 75 135. 5 15. 7 74. 9 24. 7 10 90 111. 5 s. s 59. 7 1a. 0 0 100 15.0 4.5 55.5 5.5 95 5 s. 3 42. 5 s5. 9 52. 9 s5 15 114. s 40. s 79.5 50. 2 70 30 129. 9 as. 1 81.7 55. 5 45 131. 9 44. 3 s7. 4 55. 4 40 50 153. 2 33. 3 so. 0 49. 2 25 75 151. 5 20. 9 71. 5 30. s 10 90 105. 7 7. s 55. 5 11. 5 0 100 8.5 5.2 55.5 7.5 95 5 15. 0 43. 3 s0. 4 53. 9 55 15 119. 5 40. a 51.1 59. 5 30 150. 0 49. 4 79. 0 73. 0 55 45 141. 7 42. s so. 5 55. 2 40 50 151. 2 2s. 5 77. 4 42. 1 25 129. 7 15. 9 57. 0 24. 9 10 154. 5 8.8 55. a 13. 0 0 100 24.5 4.5 55.5 5.7 5 20. 7 47. 0 7s. 2 59. 4 s5 15 152. 9 41. 5 s1. 5 51. 4 70 30 168. 3 45. 0 so. 9 57. 9 55 45 210. 9 41.0 79. 5 50. 5 40 50 195. 0 35. 4 so. 8 52. 2 25 75 201. 5 25. 7 75. 5 59. a 10 90 159. 3 s. 7 55. 5 12. s 0 17. 5. 5 70. 5 s. 2

5 Examples XXX V-X XX VIII The results summarized in Table 2 were obtained by phosphine oxide and up to about 20 percent by weight of a polycarboxylic acid compound of the formula H using a treating method similar to that of the preceding ex- 5 HO l amples, but With varying concentrations of the A'PO-polyj, H carboxylic acid mixtures (percent based upon the welght of the total solution). A solvent containing 75 percent I 1,1,1-trichl0roethane and 25 percent by volume of methyl O OH ethyl ketone was used. The curing temperature was held |I j, at 190 C. for 4minutes. 19 O TABLE 2 t t O c trat' n Acid Com- Size Wet Burst Dry Burst Example Number ZJ l jZ f S H I )If P bl: :Acitd in position (Seconds) Factor (p.s.1.) Factor (p.s.1.) Fold Solution otal olu ion 130. 8 23. 2 77. 0 5. 3 i1 8 81 i111 160. 2 33. 2 75. 0 20. 5 4. 0 0. 60 A 187- 6 49. 1 87. 3 90. 4 s. 0 1. A 366. 5 28. 6 s5. 5 45. s

XIX XXXXVIII wherein Examples XX (i) each of R and R is independently selected from the rou consistin of an alk lene and Using the same type of handsheets as employed n the an alkenylgane pgroup of 3 1 to carbon previous examples, but with curing times of four minutes atoms at temperatures of 120 C. and 190 C., the results sum- (ii) each of R2 and R4 is a group of the formula marized in Table 3 were obtained. The acid composition (CkH2k }H wherein k is an integer from 0 to 10 used Was Type C. and

TABLE 3 Percent Com osition of Wet Burst Example Treating S dlution KBB SIZE Wet Burst Dry Burst N b r Temp. 0.) MIT Fold N0. (sec) Factor (p.s.1.) Factor (p.s.1.) DrycBugst 1) on 1'0 APO Poly Acid 0" t 1 225 0.8 2.1 69.8 @liiillil: iti ifiio 120 349 0. 4 10. e 57. a 15. 1 XXXXI 1.50 0.50 120 278 111.9 27.7 74.4 37.2 XXXXII 1. 00 1. 00 120 355 157. 0 34. 6 s3. 7 41. 3 XxXXni' 2. 00 0. 00 190 21s 2. 7 40. 1 80.4 40. s XxXXIv 1. 90 0. 10 100 353 11. s 38.0 80. 0 47. 1 XXXXV 1.80 0.20 100 276 38.8 38.9 70.0 50.7 XXXXVY 1 70 0.30 190 335 140.9 41.1 80.0 51.3 XXXXV 1'50 0.50 100 202 194.1 43.1 77.4 55.0 XXXXVIIiIII 1. 00 1. 00 190 3 0 583. 6 47. 5 7s, 2 60. 6

I l i as my i i (iii) each of x and y is an integer of from 0 to 10; 1. A method of producing sized cellulosic-based paper f 1n said composition, the ratio of tns (l-aztndmyDphosphme oxide and polycarmaterlal whlch comprises. b0 1 d f b tzo lt 1 10 d (a) contacting said material with a composition conb h 'f mm a Ou 0 a an tainin an inert anhydrous solvent as carrier, and 6T 1g% C }f at i ureo r0 0 r i 'nto up to about 15 percent by Weight of tr1.s(1-az1r1d1nyl) effect a t O a tme 616 t phosphine oxide and up to about 20 percent by weight of a polycarboxylic acid of the formula RtCOOH) wherein n is an integer of from 2 to 6 and R is an unsaturated hydrocarbon group of from 30 to 114 carbon atoms to form an impregnated material, and (b) heating said impregnated material at a temperature of from 100 to 190 C. for a time sufiicient to effect a cure. 2. A sized paper product prepared by the method as taught in claim 1.

3. The method of claim 1 wherein the polycarboxylic acid is the thermal dimer of linoleic acid.

4. The method of claim 1 wherein the polycarboxylic acid is the thermal trimer of linoleic acid.

5. A method of producing sized cellulosic-based paper materials which comprises:

(a) contacting said material with a composition con taining an inert anhydrous solvent as carrier, and up 6. A sizing concentrate for paper treatment which comprises a mixture of tris(1-aziridinyl)phosphine oxide and a thermal polymer of linoleic acid containing from 2 to 6 carboxylic groups wherein the ratio of tris(1-aziridinyl) phosphine oxide to thermal polymer is from about 20:1

MURRAY KATZ, Primary Examiner. WILLIAM D. MARTIN, Examiner.

to about 15 percent by weight of tris(1aziridinyl) M. LUSIGNAN, Assistant Examiner. 

